Insecticidal triazolyl phosphorus compounds



United States Patent 3,230,139 INSECTICIDAL TRIAZQLYL PHOSPHORUSCOMLPOUNDS Jacques Meltzer, Kobus Wellinga, and Beruardus Gerhardus VanDen Bos, all of Van Houteuiaan, Weesp, Netherlands, assignors to NorthAmerican Philips Company, 1110., New York, N.Y., a corporation ofDelaware No Drawing. Original application Feb. 29, 1960, Ser. No.11,452, now Patent No. 3,111,525, dated Nov. 19, 1963. Divided and thisapplication Aug. 5, 1963, Ser. No.

7 Claims. (Cl. 167-33) This application is a division of co-pendingapplication Serial No. 11,452 filed February 29, 1960, now Patent No.3,11 1,525

This invention relates to new and novel phosphorus containingheterocyclic compounds, to methods of preparing these compounds and tothe use of said compounds as pesticides.

One of the most important needs in agriculture is for pesticides whichare effective against crop destroying pests such as insects, mites, andfungi and which are at the same time relatively nontoxic to warm bloodedanimals. The need for such pesticides is constantly increasing in viewof the rapidly increasing demand for agricultural products.

It is a principal object then of this invention to produce new and novelphosphorus containing heterocyclic compounds.

It is another principal object of this invention to provide new chemicalcompounds which are useful for the destruc tion of plant harmful pestsand which are relatively harmless to warm blooded animals.

According to the invention new and novel phosphorus containingheterocyclic compounds are provided. These compounds correspond to thegeneral formula:

wherein Q represents an organic radical containing a heterocyclic ringconsisting of carbon atoms and from 1 to 3 nitrogen atoms, two of saidnitrogen atoms being separated from each other by at least one of thering carbon atoms, and joined to the phosphorus atom through a ringnitrogen, X represents a member of the group consisting of sulfur andoxygen, T, represents a member of the group consisting of oxygen andsulfur, T represents a member of the group consisting of oxygen, sulfur,the radical NH and the radical NR wherein R represents an alkyl radicalcontaining from 1 to 5 carbon atoms and R and R each represent aliphatichydrocarbon radicals. The heterocyciic nucleus may be substituted orcondensed with a substituted or unsubstituted benzene nucleus. Howeverthe heterocyclic ring should have aromatic properties.

Examples of heterocyclic radicals that may be represented by Q are theradicals of pyrrole, pyrazole, imidazole, 1,2,4-triazole, indole,carbazole, benzimidazole and substituted products thereof.

These heterocyclic radicals may be substituted with alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkylamino,dialkylamino, arylamino, diarylamino, acylarnino, alkoxy, andalkylrnercapto substituents containing from 1 to 18 carbon atoms,halogen atoms preferably chlorine atoms, the nitro, amino, ureido,carboxy, carbalkoxy and sulfoue radicals. Best results are achieved whenthere are five carbon atoms in the heterocyclic ring and the ring issubstituted with one or more alkyl radicals containing from 1 to 7carbon atoms, a phenyl group and in particular an amino group.

3,230,139 Patented Jan. 18, 1966 Compounds of the invention in which Qrepresents the radicals, 3-amino-l,2,4-triazolyl; 3-amino-5-alkyl-1,2,4-triazolyl in which the alkyl group contains from 1 to 7 carbon atoms and3-amino-5-phenyl-l,2,4-triazolyl and in which R, and R are alkyl groupscontaining from 2-5 carbon atoms in particular ethyl and isopropyl havebeen found to be the most effective pesticides.

These compounds are very useful in combating plant harmful pests such asinsects and mites especially spider mites and also moulds. In addition anumber of these compounds are useful as plant growth regulators.

In particular, it has been found that the 0,0-diethyl phosphoryl and the0,0-diethyl-thionophosphoryl derivatives of 3-amino-1,2,4-triazole,5-phenyl-1,2,4-triazole and 3-amino-S-alkyl-1,2,4-triazole in which thealkyl group contains from 1 to 7 carbon atoms are effective pesticides.

The compounds of the invention may be prepared in such a manner that thephosphoryl thiophosphoryl group is introduced into the cyclic nitrogencontaining heterocyclic compound in one or two reaction stages.

Thus according to one method of the invention the heterocyclic compoundQH wherein H is the hydrogen atom attached to a ring nitrogen or thecompound QMe wherein Me is a metal atom preferably sodium or potassiumattached to a ring nitrogen and wherein Q has the indicated meaning isreacted with a compound corresponding to the general formula Ha1-P=(X)nTzRa wherein Ha-l represents a halogen atom such as iodine or fluorinebut preferably chlorine, X represents oxygen or sulfur, T, representsoxygen or sulfur, T represents oxygen sulfur, the radical =NH or theradical =NR wherein R represents an alkyl radical containing from 1 to 5carbon atoms, and n represents 0 or 1. This reaction is preferablycarried out in the presence of a hydrogen halide binding agentparticularly if the reactant QI-I is employed. If n has the value 0 inthe product TiRi TzRz

this material is oxidized or sulfurized. In another method the compound/Hal HalP=(X)s Hal Wherein Hal, X and n have their previously designatedmeanings is reacted with the compound QH or QMe and the resultantproduct whichhas the formula /Hal QI Hal is then reacted With analcoholate or a thiolate preferably a sodium alcoholate or a sodiumthiolate. The heterocyclic compound produced may be oxidized or reactedwith sulfur if ni=0 depending upon Whether X represents oxygen or sulfurin the final product.

In still another method of preparing the compounds of the invention, thecompound QH or Me is reacted with a compound corresponding to thegeneral formula:

to yield a compound corresponding to the general formula:

relate to a compound formed from 1 mol of the cyclic nitrogen containingheterocyclic compound and 1 mol of the phosphorus containingnon-heterocyclic reactant.

H 1 a Table I summarizes the data of the examples. 5 Table 11 gives thenames of the final products obtained TZRZ in the examples. and thishalogen containing heterocyclic compound is Example I then reacted Witha member 0f the group Consistmg of 6.05 g. of collidine and 8.8 g. ofdiethylphosphorylchloalcoholates and thiolates to produce a compoundcorresride were successively added to a suspension f 8 f 3- p g to thegeneral formula 10 amino-S-phenyltriazole-1,2,4 in 100 ml. ofacetonitrile.

T112 Subsequently the resulting mixture was stirred at 35- Q P:(X) 40 C.for two hours and then concentrated by evaporan tion in vacuo. Theresidue was extracted with acetone, the acetonic solution concentratedby evaporation and the Here too when n represents 0 the product isoxidized or residue, an oil was washed with petroleum ether (boilingsulfurized. range 40-60 C. Yield: 60%.

The reactions in which metal compounds of the cyclic The Examples II-XIand XVI, given in Table I, have nitrogen containing heterocycliccompound are not used, been carried out in a manner analogous to that ofExcan advantageously be carried out in the presence of a ample I.Included in Table I are also the Examples hydrogen halide binding agent.As such there may be XIII-XV which have been carried out in a manneranaused amines and particularly tertiary amines, for example logous tothat of Example XII given below. In Example trialkylamines, e.g.,trimethyland triethylamine and XV the potassium compound has been usedas starting N,N-dialkylanilines and further pyridine and particularlymaterial. homologues thereof, the picolines, lutidines and collidine InTable I are successively stated the numbers of the and mixtures of thesesubstances. examples, the starting materials, the diluting agents, the

Another group of acid-binding agents which may be reaction temperature,the yields of resulting products, employed comprises metal compounds ofsodium, potascalculated on the quantities of cyclic nitrogen containingsium, magnesium, calcium, barium and zinc, such as heterocyclic compoundused, the physical constants of the oxides, hydroxides, carbonates,bicarbonates, alcoholates resulting products. Of the physical constantsa boilingand carboxylic salts. point or a melting point is given. Theboiling point is These processes of preparing the compounds of theinindicated by F, followed by the temperinature in C. vention arepreferably carried out in the presence of a and the relative pressure inmm. of mercury. The meltsolvent for the cyclic nitrogen containingheterocyclic ing point, expressed in C., is indicated by S. compound.According to the nature of this compound In the Examples I, II, IV, V,VIII, XIV and XVI 0,0- and its substituents, a nonpolar or polar solventis chosen. diethylphosphorylchloride is used; in the Examples III, Assuch solvents there may be used for example aliphatic VI, VII, IX, XII,XIV and XV, O,o-diethylthiophos horyland aromatic hydrocarbons, forexample hexane, petrochloride, and in the Examples X and XI,0,0-di-isopropylleum ether and benzene aliphatic ethers, tertiaryamines, phosphorylchloride. for example pyridines, nitriles asacetonitrile, ketones as In the Examples I-XI collidine was used as thehydroacetone and methylethylketone, esters as ethyl acetate, algen acidbinding agent. cohol, for example methanol and ethanol, and further, Efor example, nitrobenzene, carbon tetrachloride, and dixample XIImethylformarnide. 11.7 g. of the sodium compound of indole, obtained byIn cases wherem: a metal compound of the cyclic nitrothe action ofsodium on indole, were suspended in 60 cc. gen conta ning heterocycliccompound is used as a startof acetonitrile. While stirring the resultingsuspension, a ing material, polar solvents, for example acetonitrile,are solution of 18.9 g. of 0,0-diethylthionophosphorylchloridepreferred. in 20 cc. of acetonitrile was added at about 1015 C. At

In order that the invention may be readily carried into the end of thereaction the separated sodium chloride effect it will now be describedin greater detail with referwas filtered 01f, the filtrate evaporatedand the residue ence to the examples and tables which follow. dissolvedin diethyl ether. The ethereal solution Was The values calculated forthe contents of various elewashed with water, dried on sodium sulphateand, after ments in the resulting products, given in the examples,filtration, concentrated by evaporation.

TABLE I Example Starting material Diluting Agent React. temp. Yield inPhysical Number in 0. percent constants 3-amino-5-phenyltriazole-2.1.4Acetonitril 35-40 (Oil). 3-aminotriazole-L2A Acetone 20 to 30 68 D0. 1do About 15 10 s=s2-s5 o.

3-amino 5-pentyltriazole-1.2.4 Dimetthylformamide+ About 15..-- 40(Oil).

309 one. 3-amino-5-methyltriazole-12.4.- .do About 15 i? Do.3-amino-5-pentyltriazole-1.2.4 do 100 Do. 3-amino-5-methyltriaz0le-1.24do 50 Do. 3-amino-5-ethyltriazole-1.2.4 AcetonitnL 84 Do. do do 73 Do.

3-amino-5-pentyltriazo1e-1.2.4 Diethyl ether".-- About 35 55 S=5354 C.3-aminotriazole-1.2.4 Acetonitril About 45 100 Tndnlo do About 15..-. 66F=112-114 c at 0.005 mm. do do About 15 51 F=110-112 c.

at 0.01 mm 3-amino-5-pheny1triazole-1.2.4 do -80 51 S=6365C Carbazole do60-70 63 Z-aminobenzimidazole Acetone About 50 30 S=228229C3-aminotriaz01e 1.2.4 Aeetonitrll About 20 82 S=5764 C3-ann'no-5-penty1triazole-1.2.4 Diethy1ether 35 763-arninotriazole-1-2-4 Acetonitril 60-70 64 s=10s-110 C 3-amino-5pentyltriaz01e-1. Benzen 60-70 66 5-phenyl-B-aminotriazole-l.2.4Acetonitril 60-70 S=104-105C A mixture of 8.4 g. of3-aminotriazole-1,2,4, 12.1 g. of collidine, 70 cc. of acetonitrile and17.2 g. of O-ethyl-N- dimethylamido-phosphorylchloride was stirred ofabout C. for 90 minutes. Then the solvent was distilled off and theresulting residue was extracted with benzene. The benzene solution wasconcentrated by evaporation and the obtained residue was washed withpetroleumether (boiling range 406(J C.). Yield g. (Y=82%). Meltingpoint: 5764 C.

TABLE II Product O. O-diethylphosphoryl)-3-amino-5-ethyltriaz0le-12.4.-(gO-diethylthionophosphoryl)-3-amino-5-ethyltriazole-94b-di-isopropylphosphoryl)-3amino-5-pentyltriazoleN-(0.0-di-isopropylphosphoryl)-3-aminotriazule-l.2.4.

- 0.0-diethylthionophosphoryl)indole.

O. O-diethylphosphoryl) indole.9&0-diethylthionophosphoryl)-3-amino-5-phenyltriazole N (O.O-diethionophosphoryD cnrbazole.

N-( 0. O-diethylphosphoryb-2-aminobenzimidazole.

N-1 g-ethyl-N-dimethylamidoph osphoryl) -3-arnin0triazoleN-(Oethyl-N-dimethylamidophosphoryl)-3-amino-5- pentyltriazole1.2.4.

N-(oiistlngrgpyl N-dimethylamidophosphoryl)-3-amin0triam e-N-(O-isopropyl-r -dimethylann'dophosphoryl)-Z ]-amino-5-pentyltriazole-1.2.4.

N-(O-isopropyl-N-dimethylamidophosphoryl)-3-amino-5- phenyltriazole-L2A.

The active compounds of the invention may be formulated and employed inthe conventional manner for destroying the noxious organisms. Thus theymay be mixed with solid carriers, ground to the desired particle sizeand dusted on the crops. Examples of the solid carriers that may beemployed are pipe clay, diatomaceous earth, kaolin, dolomite, talcum,gypsum, bentonite, attapulgite, kieselguhr, Celite, wood meal, tobaccodust, ground walnut shells and ground cocoanut shells. In these duststhe concentration of the active compound usually lies between about1-22% by weight.

The active compounds of the invention may also be applied to the cropsin the form of suspensions in a volatile liquid, usually water. Inpreparing such a suspension the active compound is formed into awettable powder and then dispersed in a volatile solvent such as water.In the formulation of the wettable powder the active compound is groundwith a solid carrier of the type employed in forming a dust and suitabledispersion agent such as a lignin sulfonate or a naphthalene sulfonateand/or a suitable wetting agent such as a fatty acid sulfonate, analkaryl sulfonate or an acid condensation product of the type sold underthe trademark Igepon are added. In the wettable powder the concentrationof the active compound may vary between wide limits. However, aconcentration of between about 10 to 80% by weight is usually preferred.

Finally the active compounds of the invention may be applied to thecrops in the form of emulsions in water or other volatile liquids. Inpreparing these emulsions the active compound is first formed into amiscible oil. These miscible oils contain besides the active compound awater insoluble solvent for the active compound and an emulsifier. Amongsolvents that may be employed are xylene, toluene, dioxane, aromaticpetroleum distillates such as solvent naptha, distilled tar oil,tetralene and cyclohexane and mixtures of these liquids. Among theemulsifiers that may be employed are the alkyl phenoxyglycol ethers,polyoxethylene sorbitan esters of fatty acids, polyoxyethylene-sorbitolesters of fatty acids and the emulsifiers known by the trademarks Tween,Triton and Atlox. The concentration of the active-compound in thesolvent is usually about 2-50% by weight and in the emulsion theconcentration of the active compound is usually between about 0.01 to0.5% by weight.

While we have described our invention in connection with specificembodiments and applications, other modifications thereof will bereadily apparent to those skilled in this art without departing from thespirit and scope of the invention as defined in the appended claims.

What is claimed is:

1. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally effectiveamount of a triazolyl phosphorus compound of the formula O-Ra wherein Qis 3-amino-l,2,4-triazolyl substituted in the 5 position only with up toone alkyl of 1 to 7 carbon atoms, the phosphorus is directly attached toa ring nitrogen and R and R are each alkyl of 2-5 carbon atoms.

2. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally effectiveamount of a triazolyl phosphorus compound of the formula wherein Q is3-amino-1,2,4-triazolyl substituted in the 5 position only with up toone alkyl of 1 to 7 carbon atoms, the phosphorus is directly attached toa ring nitrogen and R and R are each alkyl of 2-5 carbon atoms.

3. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally effectiveamount of a S-amino-S- phenyl-1,2,4-triazolyl phosphorus compound of theformula 0R QP 0 wherein Q is 3-amino-5-phenyl-1,2,4-triazolyl, R and Rare each alkyl of 2 to 5 carbon atoms and the phosphorus is directlyattached to a ring nitrogen.

4. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally effectiveamount of a 3-amino-5- phenyl-1,2,4- triazolyl phosphorus compound ofthe formula 0R1 Q-P=s wherein Q is 3-amino-S-phenyl-l,2,4,-triazolyl, Rand R are each alkyl of 2 to 5 carbon atoms and the phosphorus isdirectly attached to a ring nitrogen.

5. A method of destroying insects comprising contacting said insectswith an insecticidal com-position containing an insectici-dallyeffective amount of a N-(0,0- diisopropyl phosphoryl) 3 aminotriazole1,2,4 wherein the phosphorus is directly attached to a ring nitrogen ofthe triazole ring.

6. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally effectiveamount of a (N-(0,0- diethylphosphoryl)-3-amino-5-alkyl-1,2,4 triazolewherein said alkyl is of 17 carbon atoms and wherein the phosphorus isdirectly attached to a ring nitrogen.

7. A method of destroying insects comprising contacting said insectswith an insecticidal composition containing an insecticidally eflFectiVeamount of a (N-(0,0- diethylthiophosphoryl) 3 amino 5 alkyl 1,2,4triazole wherein said alkyl is of 17 carbon atoms and wherein thephosphorus is directly attached to a ring nitrogen.

References Cited by the Examiner UNITED STATES PATENTS FOREIGN PATENTSGreat Britain.

OTHER REFERENCES Chemical Abstracts, vol. 52, col. 11538, 1958. ChemicalAbstracts, Index to vol. 53, p. 2114s, 1959. Chemical Abstracts, vol.53, col. 19285, 1959.

5 Frear et al., J. of Economic Entomology, vol. 40, pp.

LEWIS GOTTS, Primary Examiner.

1. A METHOD OF DESTROYING INSECTS COMPRISING CONTACTING SAID INSECTSWITH AN INSECTICIDAL COMPOSITION CONTAINING AN INSECTICIDALLY EFFECTIVEAMOUNT OF A TRIAZOLYL PHOSPHORUS COMPOUND OF THE FORMULA